EP3305941B1 - Procédé de fabrication d'une couche sol-gel adhérente sur une surface métallique - Google Patents

Procédé de fabrication d'une couche sol-gel adhérente sur une surface métallique Download PDF

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Publication number
EP3305941B1
EP3305941B1 EP16002169.7A EP16002169A EP3305941B1 EP 3305941 B1 EP3305941 B1 EP 3305941B1 EP 16002169 A EP16002169 A EP 16002169A EP 3305941 B1 EP3305941 B1 EP 3305941B1
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Prior art keywords
sol
gel
metal
metal surface
layer
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EP16002169.7A
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German (de)
English (en)
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EP3305941A1 (fr
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Siegfried Piesslinger-Schweiger
Olaf BÖHME
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Sepies GmbH
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Sepies GmbH
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Priority to ES16002169T priority Critical patent/ES2742948T3/es
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1254—Sol or sol-gel processing
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/04—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1212—Zeolites, glasses
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1241—Metallic substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/10—Oxidising
    • C23C8/12—Oxidising using elemental oxygen or ozone
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/10—Oxidising
    • C23C8/12—Oxidising using elemental oxygen or ozone
    • C23C8/14—Oxidising of ferrous surfaces
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/40—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions
    • C23C8/42—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions only one element being applied
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/80—After-treatment

Definitions

  • the present invention relates to a method of adhering a sol-gel layer to a metal surface.
  • Sol-gel coatings are non-metallic inorganic or hybrid polymeric materials from colloidal dispersions, the so-called sols.
  • the starting materials are also referred to as precursors. From them arise in solution in first basic reactions finest particles. Special processing of the brine can produce powders, fibers, layers or aerogels.
  • the hydrolysis of precursor molecules and the condensation between resulting reactive species are the major basic reactions of the sol-gel process. The processes involved and the properties of the precursor molecules have a decisive influence on the resulting material properties.
  • the adhesion of sol-gel coatings to metal surfaces will vary widely depending on the coated metal, depending on the metal to be coated and the pretreatment.
  • sol-gel coatings are applied to stainless steels, aluminum and titanium after pretreatment by degreasing on the already existing, naturally formed oxide layers. This usually gives good results with stainless steels and titanium, with the exception of mechanically polished surfaces.
  • the coating usually for pretreatment the coating additionally applied a thin, about 1 to 3 microns thick oxide layer by electrochemical oxidation (anodizing).
  • the aim of the invention is to provide a method for adherent application of a sol-gel layer on a metal surface. This is achieved by the claimed method.
  • EP 1 816 219 A1 is a method for heat treatment of steel strips by means of direct flame heating known.
  • the EP 1 975 128 A1 discloses a process for producing a titanium oxide coating on various substrates.
  • the EP 0 967 297 A1 relates to a process for producing articles provided with a coating of a silica film.
  • a metal surface may be a smooth surface of a metal.
  • a metal surface may also be a pretreated, such as a polished or a roughened surface of a metal.
  • a metal surface may also be a surface of a metal already present with a passivation layer, such as an oxide layer.
  • the oxide layer provided on this metal surface by the method according to the invention differs from any passivation layer already present in the form of an oxide layer on the metal surface.
  • the oxygen content in the atmosphere is 22-100 vol.%, Preferably 30-90 vol.%, More preferably 40-80 vol.%.
  • the treatment of the metal surfaces is preferably carried out in a period of 1 to 20 seconds.
  • the atmosphere contains no sulfur compounds. It is also preferred that the method not include an additional step of removing organic residues from the at least one metal surface.
  • the layer thickness of the oxide layer is preferably 10 nm to 200 nm, more preferably 20 nm to 100 nm.
  • a method of adhering a sol-gel layer to a metal surface comprises forming oxide layers on metal surfaces as described above.
  • the application of the sol-gel layer usually follows directly, without further process steps being provided.
  • the method comprises, on the correspondingly treated metal surface, applying a liquid sol on the at least one metal surface, preferably by dipping, flooding, spraying or brushing, and allowing the sol to react to a gel, preferably by evaporation of the solvent.
  • a liquid sol on the at least one metal surface preferably by dipping, flooding, spraying or brushing, and allowing the sol to react to a gel, preferably by evaporation of the solvent.
  • Step of curing the gel preferably at 160 ° C to 300 ° C for a period of 10 to 45 minutes.
  • the sol further preferably comprises one or more elements selected from the group consisting of Al, Ti, Zr, Mg, Ca and Zn.
  • the layer thickness of the oxide layer is preferably 100 nm to 2 ⁇ m, more preferably 200 nm to 1.8 ⁇ m, more preferably 300 nm to 1.7 ⁇ m, even more preferably 500 nm to 1.5 ⁇ m, and even more preferably 800 nm to 1 ⁇ m.
  • a material comprising a metal having at least one oxidized metal surface and a sol-gel layer can be produced thereon.
  • the layer thickness of the oxide layer is preferably 100 nm to 2 ⁇ m, more preferably 200 nm to 1.8 ⁇ m, more preferably 300 nm to 1.7 ⁇ m, even more preferably 500 nm to 1.5 ⁇ m, and even more preferably 800 nm to 1 ⁇ m.
  • the layer thickness of the sol-gel layer is preferably about 6 ⁇ m, more preferably about 0.5-5.0 ⁇ m, more preferably 1.0-5.0 ⁇ m, or 0.5-3.0 ⁇ m, and most preferably 1.0-4.0 ⁇ m.
  • the sol-gel layer has a uniform thickness with variations of less than 10% of the layer thickness.
  • the metal is preferably selected from carbon steel, Korten steel, metal with chrome plated surfaces, metal with high gloss polished surfaces, stainless steel and aluminum.
  • oxide layers can be different and depending on the conditions under which they originated.
  • structure and properties of the oxide layers have a strong influence on the adhesion of subsequently applied sol-gel layers.
  • the chemical stability and corrosion resistance of oxide layers is an important factor influencing the permanent adhesion of sol-gel layers to oxide layers as a primer.
  • Sol-gel layers are usually not completely free of pores. These pores allow corrosive media to penetrate and attack the oxide layer. The degradation of oxide layers with low corrosion resistance can lead to later detachment of the sol gel layers.
  • the step of forming an oxide layer on a metal surface comprises treating the metal surfaces at high temperatures in the range of preferably 800 ° C to 1200 ° C, more preferably 1000 ° C to 1200 ° C, in combination with a rich oxygen supply of over 22 vol .-%, ie an oxygen content higher than that of the earth's atmosphere, preferably from 22 to 100 vol%, more preferably from 30 to 90 vol%.
  • the appropriate temperature is chosen depending on the metal to be coated and its surface quality.
  • the oxygen content in the atmosphere is therefore 22-100 vol .-%, preferably 30-90 vol .-%.
  • the treatment is preferably carried out either by treatment with a gas flame (flaming), which has a marked excess of oxygen and thus has a strong oxidizing effect, or by treatment by means of an oxygen plasma.
  • a gas flame the other components that are used in the combustion in the flame and make up the atmosphere, fuels such as propane, butane, a propane / butane mixture, hydrogen, methane.
  • the duration of the treatment is 1 to 10 seconds. In this case, only a thin layer of material is heated on the surface, without the underlying metal undergoes significant changes.
  • the treatment of the metal surfaces is preferably carried out in a period of 1 to 10 seconds.
  • the oxygen-excess atmosphere does not contain sulfur compounds.
  • gases for flame treatment are gases which have no components of sulfur or sulfur compounds. These can lead to the formation of metal sulfides and impair the coatability.
  • oxide layers from atmospheric plasma are not suitable for pretreatment since the high nitrogen content of around 78% by volume in the natural atmosphere leads to the embroidering of the metal surfaces. Subsequently, no firmly adhering sol-gel layer can be applied to these surfaces.
  • Another advantage of the treatment according to the invention is that organic residues on surfaces to be coated, which may adversely affect the adhesion of the coatings, are also reliably eliminated. Therefore, in just one step, both the metal surface can be prepared with an oxide layer, as well as organic residues are removed, so that a simplified process is provided. Therefore, it is preferred that the method not include an additional step of removing organic residues from the at least one metal surface.
  • the method of the invention preferably comprises applying the liquid sol on the at least one metal surface by immersion, flooding, spraying or brushing, and reacting the sol to a gel by evaporation of the solvent and curing of the gel, preferably at 160 ° C to 300 ° C for a period of 10 to 45 minutes.
  • the sol further preferably comprises one or more elements selected from the group consisting of Al, Ti, Zr, Mg, Ca and Zn.
  • Sol-gel layers on surfaces treated according to the invention are distinguished by a significantly improved adhesive strength and homogeneity in comparison to sol-gel layers on conventionally pretreated surfaces.
  • test methods such as the Rockwell test, the cross cut test, the scratch hardness test, the pull-off test or the bending test are used.
  • VDI Guideline 3198 In the Rockwell test (VDI Guideline 3198) a diamond cone with a defined force is pressed into the layer surface. In the vicinity of the hardness impression, the layer is damaged, which can be seen in the microscope as a crack network or as a layer eruptions in the edge region of the impression.
  • the evaluation of the flaking around the impression can either be done according to the VDI Guideline 3198 by division into classes 1-6, or by digital image analysis of the chipped area shares, which gives a more objective and finely subdivided rating.
  • the adhesive strength is determined by making continuous cuts at right angles to each other down to the substrate so that a grid is formed.
  • the scratch hardness test used to evaluate the adhesion of organic layer systems, such as e.g. Paints and paints used on flat, smooth sample plates
  • the sample material is applied with a uniform layer thickness on flat test plates with the same surface finish.
  • the adhesive strength is determined by passing the sheets against a rounded pin or chisel that is loaded with weights until the paint layer detaches from the substrate.
  • the pull-off test determines the minimum tensile force needed to peel or tear off a single-coat or multi-layer finish perpendicular to the surface.
  • this method loads the coating with maximum tensile force.
  • a dolly is glued vertically to the coating.
  • a tester is attached to the anvil and aligned to create a voltage perpendicular to the test area. The force is gradually increased and observed controlled until the coating surface goes off or a certain value is reached.
  • coated metal sheets with a defined radius are bent through a mandrel by 90 °, depending on the sheet thickness D (x times D). Detected is the starting radius from which the coating peels off in the bending area.
  • the multiplier serves as a parameter.
  • a second parameter is the value by how many degrees the sheet can be bent beyond 90 ° without the coating peeling off.
  • sol-gel layers By means of flame treatment or oxygen plasma, firmly adhering sol-gel layers can also be achieved on carbon steel, Korten steel and chrome-plated surfaces as well as on mechanically polished surfaces on stainless steel and aluminum.
  • a sol-gel layer is first applied in the form of a liquid sol having colloidal particles suspended therein, which subsequently converts to a gel and eventually forms a solid, hard lacquer layer. So if the "application of the sol-gel varnish” or the “hardening of the sol-gel varnish” is mentioned, the expert knows in which state the sol-gel system is located.
  • Sol-gel coatings usually consist of two reaction components, which are mixed in a fixed ratio shortly before processing. This mixture is last added as a third component, a dilution, usually an alcohol. Dilution sets the concentration of the reaction mixture and the viscosity of the final batch.
  • the sol-gel is preferably a silica sol based on silanes which are dissolved in solvents, wherein the silica sol preferably also contains one or more further sol-forming elements, preferably one or more elements from the group consisting of Al, Ti, Zr, Mg, Ca and Zn, these elements replacing the Si atoms in the colloidal structures.
  • Preferred sol-gel coatings / sol-gel coatings are in EP 2145980 described. Reference is made in particular to the in EP 2145980 described sol-gel coatings and the method for their use.
  • the hydrolyzable radicals OR ' are hydroxy, alkoxy and / or cycloalkoxy radicals. Suitable examples thereof include, for example, hydroxy, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, i-butoxy, t-butoxy, pentoxy, hexoxy, cyclopentyloxy, cyclohexyloxy, in particular Ethoxy, n-propoxy and isopropoxy are preferred.
  • the hydrolyzable radicals OR ' may be identical or different from one another.
  • the non-hydrolyzable radicals R " are alkyl and / or cycloalkyl radicals, suitable examples of which include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, pentyl, hexyl, cyclopentyl, cyclohexyl radicals, with particular preference being given to methyl, ethyl, n-propyl and isopropyl radicals
  • the nonhydrolyzable radicals R " may likewise be identical or different from one another.
  • a preferred sol-gel layer may include the starting materials TEOS (tetraethoxyorthosilane) and MTES (methyltriethoxysilane) and / or DMDES (dimethyldiethoxysilane).
  • the starting compounds are partially hydrolyzed to the corresponding hydroxy compounds (such as orthosilicic acid, trihydroxyalkylsilane, etc.), which can be promoted by the addition of a catalyst such as acid. Due to the high tendency for condensation of these hydroxy compounds, these can now condense with elimination of water to form smaller siloxane networks.
  • the sol already contains colloidal particles containing siloxane bonds. Siloxane bonds are bonds of the form ⁇ Si-O-Si ⁇ , where " ⁇ " symbolizes any three independent bonds with other elements, in particular OH, OR 'and R ", thus forming a three-dimensional crosslinked structure in the colloidal particles Where OR 'and R "have the same meaning as above.
  • the application of the sol-gel lacquer can be done in any way, such as by immersion, flooding, spraying or brushing. Preferably, however, it is done by spraying, since this allows precise control of the amount applied per unit area.
  • a sol-gel layer may have a layer thickness of up to about 6 ⁇ m, or about 0.5-5.0 ⁇ m, preferably 1.0-5.0 ⁇ m, or 0.5-3.0 ⁇ m and most preferably 1.0-4.0 microns.
  • the sol-gel layer has a uniform thickness with variations of preferably less than 10% of the layer thickness.
  • the viscosity of the sol-gel varnish can be adjusted by a person skilled in the art. It is known that the sol, with a correspondingly high dilution in its solvent, is sufficiently low-viscosity to penetrate into any pores of a surface which may be present. It is known that the sol, with a correspondingly high dilution in its solvent, is sufficiently low-viscosity to be applied by spraying, spraying, rolling or brushing.
  • Suitable solvents for the sol are water and especially alcohols such as methanol, ethanol, n-propanol or isopropanol, with ethanol and isopropanol being preferred because of their physical properties and the low toxicity of their vapors.
  • the applied sol is allowed to react to a gel.
  • This reaction converts the liquid sol into a solid gel layer, in which the colloidal particles of the sol crosslink with each other and with not yet hydrolyzed and condensed starting compounds by further hydrolysis and condensation. This can be done, for example, by evaporation of the alcoholic solvent during drying.
  • the sol-gel coatings can be baked become, thereby forming a glass-ceramic structure that is firmly adhering, resistant to aging and insensitive to environmental influences.
  • the baking of the coating can be carried out by a person skilled in the art according to the usual procedure.
  • the gel-coated surfaces will undergo thermal curing, e.g. 250 ° C subjected. This occurs at elevated temperatures, with the gel transforming into a colorless, transparent, glassy layer.
  • the silica sol constituents convert into an even more highly crosslinked silica which, depending on the composition of the underlying sol, may contain other constituents such as aluminum oxide, titanium oxide or zirconium oxide. These layers are hard, closed and resistant to many of the chemicals that a surface may come into contact under ordinary circumstances, and to temperatures up to about 500 ° C.
  • the coated surface is exposed in the subsequent curing of the gel temperatures of 160 ° C to 300 ° C, more preferably from 160 ° C to 250 ° C and more preferably from 160 ° C to 220 ° C.
  • This curing should be for a period of at least 10 minutes, preferably 20 to 45 minutes, for example 30 minutes.
  • the curing is preferably carried out at temperatures between 180 ° C and 250 ° C, for example at 200 ° C, but also temperatures below 180 ° C are suitable for this purpose.
  • the gel transforms into a hard, colorless and transparent, vitreous lacquer that tightly seals the surface, has no cracks and gives the surface high hardness and wear resistance.
  • the processes of gel formation and the curing of the gel can merge into one another, since, for example, gelation by drying and evaporation of the solvent can at least partly also take place at the beginning of the treatment for hardening. Also, such a method in which the processes of gelation and curing of the gel merge into one another, is encompassed by the invention.
  • the invention also relates to a treated surface Korten steel containing a colorless, transparent, coating on a surface of the Korten steel, the surface treatment being by a process according to the present invention Invention is performed.
  • the Korten steel according to the invention differs structurally from known Korten steels, which is recognizable by the color and the properties, such as stability against corrosion.
  • the invention also provides a metal comprising an oxidized metal surface produced by a method as described above.
  • the layer thickness of the oxide layer is preferably 100 nm to 2 ⁇ m, more preferably 200 nm to 1.8 ⁇ m, more preferably 300 nm to 1.7 ⁇ m, even more preferably 500 nm to 1.5 ⁇ m, and even more preferably 800 nm to 1 ⁇ m.
  • the invention also provides a material comprising a metal having at least one oxidized metal surface and a sol-gel layer thereon, wherein the material has been produced according to a method described above.
  • the layer thickness of the oxide layer is preferably 100 nm to 2 ⁇ m, more preferably 200 nm to 1.8 ⁇ m, more preferably 300 nm to 1.7 ⁇ m, even more preferably 500 nm to 1.5 ⁇ m, and even more preferably 800 nm to 1 ⁇ m.
  • the layer thickness of the sol-gel layer is preferably about 6 ⁇ m, more preferably about 0.5-5.0 ⁇ m, more preferably 1.0-5.0 ⁇ m, or 0.5-3.0 ⁇ m, and most preferably 1.0-4.0 ⁇ m.
  • the sol-gel layer has a uniform thickness with variations of less than 10% of the layer thickness.
  • the metal is preferably selected from carbon steel, Korten steel, metal with chrome plated surfaces, metal with high gloss polished surfaces, stainless steel and aluminum.
  • a stainless steel sheet of size DIN A5 of 1 mm thickness of material 1.4301 with a mechanically mirror-polished surface was cleaned in a dipping degreasing, rinsed with water, dried in air and spray-coated with a sol-gel layer. Subsequently, the surface was cured for 30 minutes at a temperature of 250 ° C in air.
  • the coating After cooling, the coating could be rubbed in places with the thumb. In a bending test at 90 ° with a bending radius of 5 times the sheet thickness, the coating completely dissolved in the area of deformation.
  • Example 1 A stainless steel sheet according to that in Example 1 was degreased like this and dried. Subsequently, the surface was exposed to an oxygen-rich (blue) gas flame for a period of 3 seconds and, after cooling, spray-coated with a sol-gel layer. Subsequently, the surface was cured for 30 minutes at a temperature of 250 ° C.
  • the coating was firmly adherent and could not be rubbed off with the thumb.
  • the coating showed no separation or cracking in the area of deformation.
  • the layer was wiped off the surface of the surface with a finger.
  • the coating completely dissolved in the bending area.
  • a sheet of Korten steel as in the example was cleaned in a Tauchentfettung, rinsed with water and dried. It was then flashed for 5 seconds with an oxygen-rich (blue) gas flame. After cooling The coating was firmly adherent and could not be rubbed with the thumb. In a bending test by 180 ° with a radius of 5 times the sheet thickness, the coating did not peel off and showed no delamination or cracks in the bending area. In a subsequent salt spray test over a period of 400 hours, the surface showed no corrosion.
  • a sheet of Korten steel was oxidized by pretreatment in a solution of 15% hydrogen peroxide, and then a sol-gel coating was applied by spraying and baked at 250 ° C for 30 minutes.
  • Example 4 The layer could not be rubbed off with a finger and passed the bending test with a radius of 5 times sheet thickness by 90 °, without peeling off. In a subsequent salt spray test, the surface showed significant corrosion after just 40 hours.
  • the high corrosion resistance of the surface in Example 4 compared to Example 5 shows the influence of the quality of the oxide layer produced by the method according to the invention in Example 4 as the basis of the coating.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Chemically Coating (AREA)

Claims (5)

  1. Procédé d'application par adhésion d'une couche de sol-gel sur une surface métallique, comprenant les étapes consistant à :
    - produire une couche d'oxyde sur une surface métallique par traitement de la surface métallique à une température de 600 °C à 1500 °C dans une atmosphère ayant une teneur en oxygène de 22 à 100 % en volume ou au moyen d'un plasma d'oxygène,
    - appliquer un sol liquide sur la surface métallique, le sol comprenant des silanes qui sont dissous dans un solvant et sont de formule Si(OR')4-nR"n, avec n = 0,1 ou 2, chaque OR' représentant indépendamment un radical hydroxy, alcoxy et/ou cycloalkoxy et chaque R" représentant indépendamment, si présent, un radical alkyle et/ou cycloalkyle,
    - laisser le sol réagir pour former un gel par évaporation du solvant et laisser durcir le gel.
  2. Procédé d'application par adhésion d'une couche de sol-gel sur une surface métallique selon la revendication 1, caractérisé en ce que la teneur en oxygène dans l'atmosphère est de 30 à 90 % en volume.
  3. Procédé d'application par adhésion d'une couche de sol-gel sur une surface métallique selon la revendication 2, dans lequel la teneur en oxygène dans l'atmosphère est de 40 à 80 % en volume.
  4. Procédé d'application par adhésion d'une couche de sol-gel sur une surface métallique selon l'une des revendications 1 à 3, dans lequel le traitement des surfaces métalliques est effectué pendant une période de 1 à 10 secondes.
  5. Procédé d'application par adhésion d'une couche de sol-gel sur une surface métallique selon l'une quelconque des revendications précédentes, dans lequel le métal est choisi parmi l'acier au carbone, l'acier Corten, un métal avec des surfaces chromées, un métal avec des surfaces polies au brillant mécaniquement, l'acier inoxydable et l'aluminium.
EP16002169.7A 2016-10-07 2016-10-07 Procédé de fabrication d'une couche sol-gel adhérente sur une surface métallique Not-in-force EP3305941B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
ES16002169T ES2742948T3 (es) 2016-10-07 2016-10-07 Procedimiento para la aplicación con resistencia adhesiva de una capa de sol-gel sobre una superficie metálica
EP16002169.7A EP3305941B1 (fr) 2016-10-07 2016-10-07 Procédé de fabrication d'une couche sol-gel adhérente sur une surface métallique

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP16002169.7A EP3305941B1 (fr) 2016-10-07 2016-10-07 Procédé de fabrication d'une couche sol-gel adhérente sur une surface métallique

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EP3305941A1 EP3305941A1 (fr) 2018-04-11
EP3305941B1 true EP3305941B1 (fr) 2019-07-03

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Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU1351499A (en) * 1997-12-04 1999-06-16 Nippon Sheet Glass Co. Ltd. Process for the production of articles covered with silica-base coats
DE19937186C1 (de) * 1999-08-06 2000-09-07 Mannesmann Sachs Ag Oxidationsbehandlung für Eisen enthaltende Metallteile, um diese mit einer Eisenoxid enthaltenden Oberflächenschicht zu versehen sowie behandeltes Metallteil
EP1975128A4 (fr) * 2006-01-20 2009-07-15 Osaka Titanium Technologies Co Procede de fabrication d'oxyde de titane
DE102006005063A1 (de) * 2006-02-03 2007-08-09 Linde Ag Verfahren zur Wärmebehandlung von Stahlbändern
EP2145980A1 (fr) 2008-07-07 2010-01-20 Poligrat Gmbh Surface d'acier noble coloré et procédé de coloration d'acier noble
DE102010037254B4 (de) * 2010-08-31 2012-05-24 Thyssenkrupp Steel Europe Ag Verfahren zum Schmelztauchbeschichten eines Stahlflachprodukts
EP2848715B1 (fr) * 2013-09-13 2018-10-31 ThyssenKrupp Steel Europe AG Procédé de fabrication d'un composant en acier revêtu d'une coiffe métallique protégeant de la corrosion

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
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ES2742948T3 (es) 2020-02-17

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